Iron-Catalyzed Amination of Sulfides and Sulfoxides with Azides in Photochemical Continuous Flow Synthesis

Abstract

A photochemical (UVA) continuous flow process for the amination of thioethers and sulfoxides was performed with trichloroethoxysulfonyl azide in the presence of catalytic iron­(III) acetylacetonate. Aromatic and aliphatic sulfilimines and sulfoximines were produced in high yields and short reaction times. The reaction with chiral sulfoxides was stereospecific, producing enantioenriched sulfoximines in excellent yields.

Batch and Continuous‐Flow Iron(II)‐Catalyzed Synthesis of Sulfilimines and Sulfoximines using N‐Mesyloxycarbamates

“…Sulfilimines are typically synthesized from the corresponding thioethers using transition‐metal‐catalyzed amination reactions . Related methods are used to prepare sulfoximines;– in addition, novel amination precursors and metal‐free processes have also emerged, namely for the synthesis of NH‐sulfoximine derivatives. Among delineated synthetic methods, techniques using iron complexes have stood out due to the breadth of substrate scope and the low cost of the catalyst (Scheme ).…”

Three‐Dimensional Heterocycles by Iron‐Catalyzed Ring‐Closing Sulfoxide Imidation

“…In many cases, organoazides have been applied as nitrene precursors, which is attractive because molecular nitrogen is the only byproduct being released during substrate activation . We and others used combinations of iron catalysis and organoazides in sulfur imidations . As a result, sulfilimines and sulfoximines were obtained, which proved interesting for asymmetric synthesis and applications in crop protection and medicinal chemistry .…”

Hydroxylamin‐abgeleitetes Reagenz als duales Oxidationsmittel und Aminogruppendonor für die eisenkatalysierte Herstellung von ungeschützten Sulfinamiden aus Thiolen

“…Sulfonamide, Sulfoximine und Sulfimide (Schema 1) sind für die Medizinialchemie und den Pflanzenschutz von großer Bedeutung, da sie interessante Bioaktivitäten aufweisen [1, 7–10] . Diese aufregenden Anwendungen wurden durch die Entwicklung effizienter Strategien für ihre Synthese ermöglicht [7, 8, 11–19] …”